Method of replacing one amino group in phenyl-azo-alpha-alpha-diamino pyridine with alpha hydroxyl group



Patented May 3, 1932 UNITED STATES PATENT OFFICE EIOMOND T. TISZA OFYORK, AND BERNARD JOOS, OF YONKERS, NEW YORK, AS-

SIGNORS TO THE PYRIDIUM CORPORATION, OF NEZPERA PARK,, NEW YORK, A COR-.POIRA'IION' OF YORK.

METHOD OF REPLACING ONE AMINO GROUP IN PHENYL-AZO-ALPHA-AL1'HA-DIAMINOPYRIDINE WITH A HYDROXYL GROUP K0 Drawing.

15 the original, can be used for medicinal purposes. It has distinctbactericidal properties in vitro. When administered orally to animals,it is eliminated through the urinary tract and sterilizes the urine to acertain ex- 20 tent.

This new method of obtaining beta-phenylazo alpha hydroxyalpha-amino-pyridine directly out ofbeta-phenyl-azo-alpha-alphadiamino-pyridine is a very importantimprovement.

The method of procedure is the following Ewample l 1.0 grambeta-phenyl-azo-alpha-alpha-diamino-pyridine hydrochloride is dissolvedin 110 cc. of dilute hydrochloric acid of 2.5% and boiled on a refluxcondenser for fifty minutes. Nochange of color or precipitation wasnoted in the liquid. After fifty minutes boiling, the mixture was cooleddown, when a yellow precipitate formed. This precipitate was collectedon a filter and washed with distilled 'water. The mother liquor givesoff ammonia on addition of sodium hydroxide. To purify the precipitate,it was dissolved in 5 cc. sodium hydroxide of 40% at about 65 0., thencooled and precipitated with addition of. hydrochloric acid tillneutralreaction. The'pre cipitate was then recrystallized out ofacetone. The yield is about 60%.

Emample ll 0.86 gram betaphenyl-azo-alpha-alphadiaminopyridine wasdissolved in 110 cc. of

Application filed July 11',

1929. Serial No. 377,600.

dilute sulphuric acid of 3.5% and boiled on a reflux condenser for onehour. N 0 change of color or precipitation was noted in the liquid.After boiling for one hour, the mixture was cooled down, when a yellowprecipitate formed. This precipitate was collected on a filter andwashed with distilled water. To purify the precipitate, it was dissolvedin 5 cc. sodium hydroxide of 40% at about 65. C., then cooled andprecipitated with addition of sulphuric acid till neutral reaction. Theprecipitate was then recrystallized out of acetone.

The substance so obtained crystallizes out of acetone in yellow coloredneedles. It melts at 242 C. with decomposition. Itis very slightlysoluble in water and ether. Slightly soluble in chloroform, carbontetrachloride, or toluol. More soluble in methyl alcohol and acetone. Itis soluble with orange red color in dilute acids or alkalies forming thecorresponding acid or alkali salts. The chemical reaction of the processis the following:

H IIN:NO I HZN N on Preparing this substance by different methods, sofar gave us always the same product.

and

sult incombustion.

To prove that the" reaction product is actual 1y as described above, wemade combustions of the pure material:

The new substance. gavethe following re- 7 ler centpha-hydroxy-alpha:aniino pyridine.

Carbon; 61.65 Hydrogen 45.71 Nitrogenl "26.1 7 Oxygen A 7.4 7

. resulting dyeineachcase has the same prop erties as the; productobtained by this'new methodof replacing an amino group with by d'mxylamp in el phenyl-azoealpha-alp'ha-diamino-pyridine. T

T I I V t v I I V hese facts Venfy 1e colrec mess 'blebetafphenylazo-alph-a-hydroXy-alphanew process of replacing one aminogroup'in beta-phenyl aZo-alpha-alpha-dianiino -"pyri dine. with .ahydroxyl group.

' The reaction can be done with other mineral acids. (sulphuric, etc.)instead of hydrochloric acid, and substituted phenyl-azoealpha-alphasdiaminoepyridines may be used instead af beta-phenyl-azoalpha-al'pha diamino-pyridine. In order to obtain acid or alkali salts,it is only necessary to dissolvethe base in the acid or alkalicorresponding' -to the desired salt. As for instance, ,to' obtainthe'hydrochloride, the base is dissolvedin hydrochloric acid, or toobtain the soda salt, the base is dissolved. in sodium"hydroxidesolution. Thesesalts can be: crystallized out of therespectiyesol-utions. V

What is claimed: as new is:

1. The method of'preparing beta-phenylazo.- alpha -hydroxy alpha?-;amino pyridine, which." consists in boiling .beta-phenyl-azo;alpha-alpha-diamino-pyridineswith a dilute highly ionized mineral acid.

2. The method of preparing beta-phenylazo-alpha-hyd'roky alpha aminopyridine, which consists. boilingbeta-phenyl-azoalpha.-alpha-diamino-pyrid-i-ne with dilute (2.5% byweight) hydrochloricacid.

3. The method ofpreparing beta-phenylr azo-alpha-hyd-roxy alpha aminopyridine,

which consists'i'n replacing one amino group in beta-phenylazo-alph'aalpha-diamino-pyridines with a hydroXy group by boiling with a dilutemineral acid. 7 i

- 4. 'The method of preparing beta-phenylazo alphayhydrox'y- 1 alpha.amino pyridine,

- Per cent chloric' acid.

which consists in replacing one amino group in betaphenyl azo -alphaalpha-diaminopyridine with ahydroxy group by boiling with dilute (HQ-5%by W h lydrochloric 5. In the method ofpreparing alkali solublebeta-phenyl-azo-alpha hydroxy T alphaaniino-pyri dine from" beta-phenylazo alphaalpha-d'iaminopyridine, the step which consists in boiling'the"beta-phenyl-a'zo-alphaalpha-diamino-pyridine with dilute (2.5% by 61 Inthe method-of preparlng alkali solu- T ble beta-phenyl azo alphahydroxyalpha.

amino-pyridines from beta-phenyl-azo alp'haj alpha-diamino pyridine,.thes cep which con- 'sists in boiling the. beta-phenyl-azo-alph'adi-lutemineral acid. 1 7. In. the.- method of preparing alkali .soflluble-beta-phenyl-azo-alpha=hydroxy-alphaamino-pyridine from beta-.phenyl-azoalphaalp'ha-diainino pyridine, the-step whichconsists in boilingthebeta-phenyl;-azo-alpha alpha-diamino pyridine withdiluteihydroalpha-diamino-pyridine-with a highly ionized 8. 111 themethod of preparing alkali solu' 9. In the methodof prepariamino'pyrid'ines ifroin beta-phenyl-a'zo-alphaealpha-diamino-pyridines,the stepi which consists in'boiling thebeta-phenyl-azo-alphafalpha-diamino-pyridine with. a highly ionizeddilute mineral acid. r 10-. 'Aanedicinal substance. soluble-in. the acidfluids'of the stomach and the alkaline fluids of the intestines,including an isomer of.beta-phenyl-azo-alpha -:hyd'roxy ralphaamin'o-pyridineQ e 11'. A fmedicina'l' substance soluble -i'n theacid fluids of: the. stomach "and the "alkaline fluids of theintestines,including isomers of betaphenyl azo alpha -'hydroxy--alphaamino-pyridine. Y Y 7 I 12A medicinal substance soluble in theacidfluids of thestomach and the-alkaline fluids ofthe intestines,composed of isomers of beta-phenyl-azo-alpha 7' hydroxyalphaaminosplyri'dine hydrochloride. 13. Asa medi inali agent, the.alkali salt of beta phenyl-azo alpha hydroxy -':a1pha-.

amino-pyridine. Signed at. Yonkers, in the county of. estehester andState ofNewYork, this 2th day i ng, alkali 50111.. ble beta phenylazo-alpha-hydroxy-alpha- 17 7 ies

